EP0069443B1 - Imidazole, Verfahren zu deren Herstellung und deren Anwendung als Mittel gegen das Anlaufen von Silber - Google Patents

Imidazole, Verfahren zu deren Herstellung und deren Anwendung als Mittel gegen das Anlaufen von Silber Download PDF

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Publication number
EP0069443B1
EP0069443B1 EP82302103A EP82302103A EP0069443B1 EP 0069443 B1 EP0069443 B1 EP 0069443B1 EP 82302103 A EP82302103 A EP 82302103A EP 82302103 A EP82302103 A EP 82302103A EP 0069443 B1 EP0069443 B1 EP 0069443B1
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Prior art keywords
imidazole
dithiocarboxylic acid
methylimidazole
alkali metal
acid
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French (fr)
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EP0069443A1 (de
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Natsuo Sawa
Tokuichi Saeki
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Shikoku Chemicals Corp
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Shikoku Chemicals Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/90—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/16—Sulfur-containing compounds
    • C23F11/162—Thioaldehydes; Thioketones

Definitions

  • the present invention relates to a novel imidazole compound and a process for the synthesis thereof. More particularly, the present invention provides a novel imidazole compound having a rust preventive action to metallic silver.
  • a known imidazole compound such as 2-undecylimidazole or 2-undecyl-4-methylimidazole is effective for preventing rusting in metallic copper, but it does not exhibit any rust preventive action to metallic silver.
  • an imidazole-4(5)-dithiocarboxylic acid represented by the following general formula : wherein R 2 stands for a hydrogen atom or a residue selected from hydrocarbon groups having up to 20 carbon atoms, especially methyl, ethyl, undecyl, heptadecyl and phenyl groups, and R 4 stands for a hydrogen atom or an alkyl group having up to 4 carbon atoms, especially a methyl group, has a rust preventive action to silver.
  • the above compound has no rust preventive action to metallic copper though it has an excellent rust preventive action to metallic silver. Namely, the above compound has no rust preventive action to copper but discolors copper to a brown color. The reason for this difference between the action to silver and the action to copper has not been elucidated.
  • imidazole-4(5)-dithiocarboxylic acid compound represented by the following general formula : wherein R 2 stands for a hydrogen atom or a monovalent hydrocarbon group having up to 20 carbons, R 4 stands for a hydrogen atom or an alkyl group having up to 4 carbon atoms, and X stands for a hydrogen atom or an alkali metal atom, preferably sodium or potassium.
  • R 2 and R 4 are as defined above, and M stands for an alkali metal atom.
  • An alkali metal salt of an imidazole can easily be obtained by heating the imidazole with an equimolar amount of an alkali metal hydroxide while removing water formed by the reaction, and it can also be obtained by heating the imidazole with an equivalent amount of an alkali metal. Since an alkali metal is more expensive than its hydroxide, the latter method is not practically advantageous.
  • R 2 , R 4 and X are as defined above.
  • the alkali metal hydroxide may be used in an amount larger than 1 mole.
  • the reddish brown glutinous residue obtained after removal of the solvent by distillation is a mixture of the alkali metal salt of the imidazole-dithiocarboxylic acid and the alkali metal hydroxide.
  • reaction mixture is subjected to distillation under reduced pressure to remove the solvent by distillation, whereby the intended alkali metal salt of the imidazole-dithiocarboxylic acid containing the alkali metal hydroxide is obtained in the form of a reddish brown glutinous residue.
  • DMSO • dimethylsulfoxide
  • other solvents such as water, methanol, ethylene glycol, 1,4-butane diol, t-butanol, pyridine, a-picoline, (3-picoline, y-picoline, aldehydocollidine, triethylamine, acetonitrile, acetone, polyethylene glycol 1500, methylcellosolve (cellosolve is a registered Trade Mark), 2-ethyl-4-methylimidazole and DMF are used, better results than those obtained by DMSO cannot be obtained.
  • pyridine, picoline and acetonitrile give yields of about 80 %, but these yields are inferior to those attained by DMSO.
  • the solvent is used in an amount of 100 to 600 % by weight based on the imidazole.
  • an alkali metal hydroxide and 1 to 2 moles of carbon disulfide are used per mole of the imidazole, but it is preferred that the alkali metal hydroxide and carbon disulfide be used in amounts of 1.5 to 2.0 moles and about 1.2 moles, respectively, per mole of the imidazole.
  • alkali metal hydroxide there can be used sodium hydroxide and potassium hydroxide, but use of sodium hydroxide is preferred from the economical view-point.
  • the present reaction is an exothermic reaction, and the reaction temperature may optionally be chosen within the range of from room temperature to 150 °C. In view of the apparatus problems and the productivity, it is most preferred that the reaction be carried out at 80 to 85 °C. In this case, the reaction time is 1.5 to 3 hours.
  • the present reaction may be carried out under pressure. However, since the reaction is sufficiently advanced even under atmospheric pressure, the reaction need not be carried out particularly under pressure.
  • This alkali metal salt is easily soluble in water, but the dithiocarboxylic acid is hardly soluble in water. By utilizing these solubility characteristics, the latter compound is separated.
  • the alkali metal salt or the alkali metal salt containing the excess of the alkali metal hydroxide is dissolved in water, and active carbon is added to the aqueous solution and filtration is carried out.
  • a mineral acid is added to the filtrate until the filtrate becomes acidic.
  • the alkali metal ion is converted to a mineral acid salt to precipitate the imidazole-dithiocarboxylic acid.
  • the precipitated crystal is recovered by filtration, washed with water and dried to obtain the intended compound. If necessary, the obtained compound may be purified by recrystallization from an organic solvent.
  • the obtained intended compound is easily soluble in aqueous ammonia, if the intended compound is dissolved in aqueous ammonia and the resulting solution is subjected to concentration under reduced pressure to evaporate ammonia, the intended compound is precipitated again in the form of a crystal from the aqueous solution. If this crystal is recovered by filtration, the intended compound can be obtained in the purified form.
  • reaction formula alkali metal salt of imidazole-dithiocarboxylic imidazole-dithiocarboxylic acid acid
  • R 2 , R 4 and M are as defined above.
  • the properties of the alkali metal salt of the imidazole-dithiocarboxylic acid are as follows.
  • Each compound is an alkaline glutinous solid which is easily soluble in a polar solvent such as water and alcohol and shows a reddish brown color. Recrystallization is ordinarily difficult.
  • the alkali metal salt is used as a precursor of an ester of the dithiocarboxylic acid which has a latent utility as an agricultural chemical, an epoxy curing agent or a rubber vulcanizer or as a precursor of a metal salt of the dithiocarboxylic acid which has a latent utility as an agricultural chemical.
  • the alkali metal salt is once converted to the imidazole-dithiocarboxylic acid by the acidifying treatment, the dithiocarboxylic acid is dissolved in an aqueous solution containing an equivalent amount of an alkali metal hydroxide and the aqueous solution is concentrated to the solid under reduced pressure to obtain the intended compound in the purified form. According to this method, purification can be accomplished more easily than according to the recrystallization method.
  • TLC thin layer chromatography
  • imidazole-dithiocarboxylic acids are as follows.
  • Brown crystal weakly acidic, melting point of 154-157°C, hardly soluble in water, methanol, chloroform, acetic acid and acetone, easily soluble in DMSO and aqueous NaOH
  • Reddish violet crystal neutral, melting point of 177-178.5 °C, hardly soluble in water, methanol, ethanol and acetone, soluble in acetic acid, easily soluble in DMF and DMSO
  • dithiocarboxylic acid is dissolved in an appropriate organic solvent (for example, methanol) and the surface of surface-polished silver is contacted with the solution (coating, spraying and dipping methods may be adopted). Then, the solvent adhering to the surface is evaporated. Even when the so-treated surface of silver is allowed to stand in air for a long time, blackening is not caused to occur at all.
  • an appropriate organic solvent for example, methanol
  • a paste may be prepared by mixing the above-mentioned solvent solution of the dithiocarboxylic acid with an appropriate abrasive, and a rust preventive effect can be attained by polishing the surface of silver with this paste. Since this polishing treatment includes contacting the solution with the surface of silver, this method is included within the scope of the present invention.
  • a branched flask (carbon dioxide gas in air was shut off by attaching a soda lime drying tube to the flask) was charged with 0.1 mole (11 g) of 2-ethyl-4-methylimidazole and 0.1 mole (4.0 g) of NaOH, and they were heated by an alcohol lamp while removing formed water by distillation. When distillation of formed water terminated, heating was stopped and the reaction product was naturally cooled. The so-obtained sodium salt of the imidazole was a solid mass, and it was difficult to withdraw the product from the flask. Accordingly, the product was broken and pulverized promptly together with the flask and charged into a reaction vessel equipped with a reflux cooler and a soda lime tube. Then, 38 ml of t-butanol was added and the mixture was heated on an electric heater equipped with an electromagnetic stirrer until reflux started.
  • the precipitated crystal was recovered by filtration, washed with water and dried to obtain 12.3 g (the yield being 66 % based on the imidazole) of crude 2-ehtyl-4-methylimidazole-5-dithiocarboxylic acid (having a melting point of 170-172 °C).
  • the precipitated crystal was recovered by filtration, washed with water and dried to obtain 8.6 g (the yield was 92.5 % based on the imidazole) of crude 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid having a melting point of 171-173 °C.
  • a reaction vessel equipped with a reflux cooler and a soda lime tube was charged with 0.1 mole (11.0 g) of 2-ethyl-4-methylimidazole, 0.1 mole (5.6 g) of KOH and 38 ml of t-butanol, and the mixture was heated on an electric heater equipped with an electromagnetic stirrer until reflux started. Then, 0.12 mole (9.1 g) of carbon disulfide was dropped into the mixture over a period of 20 minutes and reflux was continued for 2.6 hours. Then, the reaction mixture was cooled and subjected to concentration under reduced pressure, and the residue was dissolved in 100 ml of water and active carbon was added to the solution. Then, the solution was filtered and the filtrate was acidified with hydrochloric acid.
  • the precipitated crystal was recovered by filtration, washed with water and dried to obtain 7.6 g (the yield was 41 % based on the imidazole) of crude 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid having a melting point of 167 to 169 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that p-picoline was used instead of ⁇ -picoline, to obtain 7.8 g (the yield was 84 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 169 to 170 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that ⁇ -picoline was used instead of ⁇ -picoline, to obtain 7.7 g (the yield was 83 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 168 to 169 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that aldehydocollidine was used instead of «-picoline, to obtain 7.2 g (the yield was 77 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 169 to 171 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that acetonitrile was used instead of ⁇ -picoline, to obtain 7.6 g (the yield was 81 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 169 to 171 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that acetone was used instead of ⁇ -picoline and the reaction temperature was changed to 60 to 65 °C, to obtain 7.4 g (the yield was 79 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 167 to 169°C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that 2-ethyl-4-methylimidazole was used instead of a-picoline and the concentration under reduced pressure was omitted, to obtain 7.9 g (the yield was 85% based on carbon disulfide) of the corresponding dithiocarboxylic acid having a melting point of 168 to 170°C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that DMSO was used instead of ⁇ -picoline and the reaction temperature was changed to 25 to 30 °C, to obtain 8.4 g (the yield was 90% based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 170 to 172 °C.
  • Example 5 Procedure of Example 5 was repeated in the same manner except that DMSO was used instead of ⁇ -picoline and the amount of NaOH was changed to 0.075 mole from 0.1 mole, to obtain 8.84 g (the yield was 95 % based on the imidazole) of the corresponding dithiocarboxylic acid having a melting point of 171 to 173°C.
  • Example 15 Procedure of Example 15 was repeated in the same manner except that 0.7 mole (10.08 g) of 2-phenylimidazole was used instead of 2-phenyl-4-methylimidazole, to obtain 14.5 g (the yield was 94 % based on the imidazole) of 2-phenylimidazole-4(5)-dithiocarboxylic acid having a melting point of 150 to 153 °C.
  • Example 15 Procedure of Example 15 was repeated in the same manner except that 0.07 mole (15.54 g) of 2- undecylimidazole was used instead of 0.07 mole of 2-phenyl-4-methylimidazole, to obtain 17.4 g (the yield was 83 % based on the imidazole) of 2-undecylimidazole-4(5)-dithiocarboxylic acid having a melting point of 108 to 114 °C.
  • Example 15 Procedure of Example 15 was repeated in the same manner except that 0.07 mole (6.72 g) of 2,4-dimethylimidazole was used instead of 0.07 mole of 2-phenyl-4-methylimidazole, to obtain 11.1 g (the yield was 92 % based on the imidazole) of 2,4-dimethylimidazole-5-dithiocarboxylic acid having a melting point of 185 to 187 °C.
  • Example 19 Procedure of Example 19 was repeated in the same manner except that 0.09 mole (7.38 g) of 4-methylimidazole was used instead of 0.09 mole of imidazole, to obtain 3.65 g (the yield was 26 % based on the imidazole) of 4-methylimidazole-5-dithiocarboxylic acid having a melting point of 151 to 154 °C.
  • Example 19 Procedure of Example 19 was repeated in the same manner except that 0.09 mole (8.64 g) of 2-ethylimidazole was used instead of 0.09 mole of imidazole, to obtain 9.6 g (the yield was 62 % based on the imidazole) of 2-ethylimidazole-4(5)-dithiocarboxylic acid having a melting point of 134 to 138 °C.
  • a mixture of 0.05 mole (5.5 g) of 2-ethyl-4-methylimidazole and 0.05 mole (2.0 g) of NaOH was treated in the same manner as described in Example 1 to form the corresponding sodium salt of the imidazole.
  • the sodium salt was reacted with 0.06 mole (4.6 g) of carbon disulfide in 19 ml of DMSO to obtain 7.75 g (the yield was 83 % based on the imidazole) of crude 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid having a melting point of 171 to 172 °C.
  • Example 22 Procedure of Example 22 was repeated in the same manner except that the amount of DMSO was changed to 9.5 ml from 19 ml and the amount of NaOH was changed to 0.10 mole from 0.05 mole, to obtain 8.5 g (the yield was 91 % based on the imidazole) of crude 2-ethyl-4-methylimidazole-5-dithiocarboxylic acid having a melting point of 171 to 172 °C.
  • Example 19 Procedure of Example 19 was repeated in the same manner except that 0.09 mole (27.5 g) of 2- heptadecylimidazole was used instead of 0.09 mole of imidazole, to obtain 14.1 g (the yield was 41 % based on the imidazole) of 2-heptadecylimidazole-4(5)-dithiocarboxylic acid having a melting point of 107 to 112 °C.
  • the surface of a pure silver plate having a width of 1.5 cm and a length of 10 cm was polished and washed with acetone, and the right half portion of the surface was lightly wiped with gauze impregnated with the above solution and the silver plate was allowed to stand still in a room.
  • the left half of the surface was gradually discolored but the right half was kept lustrous. When 30 days had passed, the left half was completely blackened while the right half was kept lustrous.
  • 2-Phenyl-4-methylimidazole-5-dithiocarboxylic acid was dissolved in ethanol to form a solution having a concentration of 0.1 % (wt/v), and the test was carried out in the same manner as described in Example 26. When 30 days had passed, the left half of the surface of the silver plate was completely blackened while the right half was kept lustrous.
  • 2-Phenylimidazole-4(5)-dithiocarboxylic acid was dissolved in ethanol to form a solution having a concentration of 0.1 % (wt/v).
  • the test was carried out in the same manner as described in Example 26. When 30 days had passed, the left half was completely blackened while the right half was kept lustrous.
  • 2-Heptadecylimidazole-4(5)-dithiocarboxylic acid was dissolved in ethanol to form a solution having a concentration of 0.1 % (wt/v).
  • the test was carried out in the same manner as described in Example 26. When 30 days had passed, the left half was completely blackened while the right half was kept lustrous.
  • 2-Ethylimidazole-4(5)-dithiocarboxylic acid was dissolved in ethanol to form a solution having a concentration of 0.1 % (wt/v).
  • the test was carried out in the same manner as described in Example 26. When 10 days had passed, the left half was discolored to yellowish brown while the right half was kept lustrous.
  • 2,4-Dimethylimidazole-5-dithiocarboxylic acid was dissolved in methanol to form a solution having a concentration of 0.1 % (wt/v).
  • the test was carried out in the same manner as described in Example 26. When 10 days had passed, the left half was discolored to yellowish brown while the right half was kept lustrous.
  • 2-Methylimidazole-4(5)-dithiocarboxylic acid was dissolved in ethanol to form a solution having a concentration of 0.1 % (wt/v).
  • the test was carried out in the same manner as described in Example 26. When 10 days had passed, the left half was discolored in yellowish brown while the right half was kept lustrous.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (14)

1. Imidazol-4(5)-dithiocarbonsäureverbindung der allgemeinen Formel
Figure imgb0033
worin R2 ein Wasserstoffatom oder einen einwertigen Kohlenwasserstoffrest mit bis zu 20 Kohlenstoffatomen darstellt, R4 ein Wasserstoffatom oder einen Alkylrest mit bis zu 4 Kohlenstoffatomen bedeutet und X ein Wasserstoffatom oder ein Alkalimetallatom darstellt.
2. Verbindung nach Anspruch 1, worin R2 einen Methyl-, Ethyl-, Undecyl- oder Heptadecylrest bedeutet.
3. Verbindung nach Anspruch 1 oder Anspruch 2, worin X für Natrium oder Kalium steht.
4. Verbindung nach einem der voranstehenden Ansprüche, worin R4 einen Methylrest bedeutet.
5. Verbindung nach Anspruch 1, ausgewählt unter Imidazol-4(5)-dithiocarbonsäure, 2-Methylimidazol-4(5)-dithiocarbonsäure, 2-Ethylimidazol-4(5)-dithiocarbonsäure, 2-Undecylimidazol-4(5)-dithiocarbonsäure, 2-Heptadecylimidazol-4(5)-dithiocarbonsäure, 2-Phenylimidazol-4(5)-dithiocarbonsäure und die Natriumsalze davon.
6. Verbindung nach Anspruch 1, ausgewählt unter 4-Methylimidazol-5-dithiocarbonsäure, 2,4-Dimethylimidazol-5-dithiocarbonsäure, 2-Undecyl-4-methylimidazol-5-dithiocarbonsäure, 2-Phenyl-4-methylimidazol-5-dithiocarbonsäure, den Natriumsalzen davon, und 2-Ethyl-4-methylimidazol-5-dithiocarbonsäure und dessen Kaliumsalz.
7. Verfahren zur Herstellung einer Imidazol-4(5)-dithiocarbonsäureverbindung nach Anspruch 1, worin eine Imidazolverbindung der allgemeinen Formel
Figure imgb0034
worin R2 und R4 die in Anspruch 1 genannte Bedeutung haben, mit Kohlenstoffdisulfid und einem Alkalimetallhydroxid in Gegenwart eines Lösungsmittels umgesetzt wird und gegebenenfalls die erhaltene Imidazolverbindung acidifiziert wird.
8. Verfahren nach Anspruch 7, worin das Alkalimetallhydroxid Natriumhydroxid oder Kaliumhydroxid ist.
9. Verfahren nach Anspruch 7 oder 8, worin das Lösungsmittel Dimethylsulfoxid, Pyridin, ein Picolin oder Acetonitril ist.
10. Verfahren nach einem der Ansprüche 7 bis 9, worin die Reaktion bei einer Temperatur von Raumtemperatur bis 150 °C durchgeführt wird.
11. Verfahren zur Herstellung einer Imidazol-4(5)-dithiocarbonsäureverbindung gemäß Anspruch 1, worin ein Imidazol-Alkalimetallsalz der allgemeinen Formel
Figure imgb0035
worin R2 und R4 die in Anspruch 1 angegebene Bedeutung haben und M ein Alkalimetallatom darstellt, mit Kohlenstoffdisulfid in Gegenwart eines Lösungsmittels umgesetzt wird und gegebenenfalls die erhaltene Imidazolverbindung acidifiziert wird.
12. Verfahren zur Verhinderung des Anlaufens von metallischem Silber, worin eine Lösung einer Imidazol-4(5)-dithiocarbonsäure gemäß Anspruch 1 gelöst in einem organischen Lösungsmittel auf die Oberfläche des metallischen Silbers aufgebracht wird.
13. Lösung zur Verwendung bei der Verhinderung des Anlaufens von metallischem Silber, die eine Imidazol-4(5)-dithiocarbonsäure gemäß Anspruch 1 gelöst in einem organischen Lösungsmittel enthält.
14. Poliermittel zur Verwendung bei der Verhinderung des Anlaufens von metallischem Silber, welches ein Gemisch einer Lösung gemäß Anspruch 13 und eines Scheuermittels enthält.
EP82302103A 1981-04-23 1982-04-23 Imidazole, Verfahren zu deren Herstellung und deren Anwendung als Mittel gegen das Anlaufen von Silber Expired EP0069443B1 (de)

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JPS6029707B2 (ja) * 1981-04-23 1985-07-12 四国化成工業株式会社 新規イミダゾ−ル化合物，該化合物の合成法および該化合物を用いる銀金属の防錆方法

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KR870000675B1 (ko) 1987-04-06
US4394511A (en) 1983-07-19
JPS57176965A (en) 1982-10-30
KR830010078A (ko) 1983-12-26
JPS6029707B2 (ja) 1985-07-12
DE3261180D1 (en) 1984-12-13
US4431818A (en) 1984-02-14
US4469622A (en) 1984-09-04
EP0069443A1 (de) 1983-01-12

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